Subcooled Liquid Density Measurements and PvT Measurements in

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Subcooled Liquid Density Measurements and PvT Measurements in the Vapor Phase for trans-1,3,3,3-Tetrafluoroprop-1-ene (R1234ze(E)) J. Steven Brown,† Giovanni Di Nicola,‡ Claudio Zilio,§ Laura Fedele,*,∥ Sergio Bobbo,∥ and Fabio Polonara‡ †

Department of Mechanical Engineering, The Catholic University, Washington, District of Columbia, United States Dipartimento di Energetica, Università Politecnica delle Marche, via Brecce Bianche 12, 60131 Ancona, Italy § Dipartimento di Ingegneria Industriale, Università degli Studi di Padova, Padova, I-35131, Italy ∥ Istituto per le Tecnologie della Costruzione, Consiglio Nazionale delle Ricerche, Corso Stati Uniti 4, 35131 Padova, Italy ‡

S Supporting Information *

ABSTRACT: Some 14 099 subcooled liquid density data and 160 vaporphase PvT data for trans-1,3,3,3-tetrafluoroprop-1-ene (R1234ze(E)) are presented. The subcooled liquid density data are for eight isotherms evenly separated approximately from (283 to 353) K for pressures from close to saturation to 35 MPa, and the vapor-phase PvT data are for nine isochores for temperatures approximately from (243 to 373) K and for pressures approximately from (57 to 1024) kPa. In addition, a saturated liquid density correlation, a Tait correlation for the subcooled liquid density data, and a Martin−Hou equation of state for the vapor phase PvT data are presented.



INTRODUCTION In recent years, a large effort has been expended on studying refrigerants with low global warming potential (GWP) primarily due to regulations, agreements, and laws, both nationally and internationally. Several fluorinated propene isomers are under investigation for which at least two are actively being pursued for commercialization: R1234yf (2,3,3,3tetrafluoroprop-1-ene; CF3CFCH2), which has a 100-year GWP of 4 compared to carbon dioxide1 and is a possible replacement for R134a in mobile applications, 2 and R1234ze(E) (trans-1,3,3,3-tetrafluoroprop-1-ene; CF3CH CHF), which has a 100-year GWP of 6 compared to carbon dioxide3 and is being considered as a potential alternative blowing agent, propellant, and refrigerant.4 Note that R134a has a 100-year GWP compared to carbon dioxide of 1430.5 Thermophysical property data and related equations of state (EoS) for these two isomers have begun to appear but are rather limited. Because of this, the authors of this paper have recently begun investigations of these two isomers. They have already published vapor-pressure data,6,7 pressure−temperature−volume data in the vapor phase,8 and subcooled liquid density data9 for R1234yf; solubility data for PAG/R1234yf mixtures;10 and vapor-pressure data11 for R1234ze(E). This paper is a continuation of this overall research effort wherein subcooled liquid densities and PvT data in the vapor phase for R1234ze(E) from two different laboratories are presented. In particular, the two laboratories are the Thermodynamic Properties Laboratory of the Istituto per le Tecnologie della © 2012 American Chemical Society

Costruzione of the Consiglio Nazionale delle Ricerche (ITC− CNR) and the Dipartimento di Ingegneria Industriale e Scienze Matematiche of the Università Politecnica delle Marche (UnivPM). While there are already some published data for R1234ze(E), there is a need for additional experimental property data. To date, experimental data are provided in the public domain for critical state properties,12 vapor pressure,11,13−16 liquid density,12−17 vapor density,13−15,18 isobaric and isochoric specific heats,17,19−21 speed of sound,22,23 surface tension,13 liquid and vapor thermal conductivities,13,24 and liquid and vapor viscosities.13,25 (Note that Matsuguchi et al.17 and Yamaya et al.21 report the same liquid density data). Several EoS also are presented: extended corresponding states (ECS) EoS,13,26 Peng−Robinson (PR) EoS,27 and FEQ Helmholtz EoS.15,28 Note that the EoS of McLinden et al.15 is incorporated in REFPROP 9.0.29 In this paper, the subcooled liquid density along eight isotherms between (283.15 and 333.15) K for pressures to 35 MPa was measured with a vibrating tube densimeter (Anton Paar DMA 512), with an estimated expanded uncertainty of approximately 0.05 %. Saturated liquid densities were estimated by extrapolating the measured densities. Correlations were developed for the measured subcooled liquid density data and Received: August 30, 2012 Accepted: October 26, 2012 Published: November 6, 2012 3710

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Density Calibration. The period of oscillation of the Utube under vacuum while filled with water was correlated for different pressures (up to 35 MPa) and temperatures of (283.15 to 353.15) K. Water was used because of the availability of the high accuracy EoS of Wagner and Pruss.32 The calibration procedure and the resulting equations are given in Fedele et al.30 The reliability of the experimental techniques and equipment has been confirmed with R134a.9 For R134a along five isotherms of (283.15, 303.15, 323.15, 343.15, and 353.15) K for P < 35 MPa, the maximum absolute deviation (Δρ/ρ = (ρcalc − ρexp)/ρcalc) relative to Tillner-Roth and Baehr33 was 100·Δρ/ρ = 0.12 %, validating the reliability of the experimental measurements. Experimental Apparatus and Procedure: UnivPM. The superheated vapor pressure measurements were taken using a constant volume apparatus consisting of a stainless steel sphere, already described in detail.34,35 Here, only the essential features are described. The spherical cell and pressure transducer were submerged in the appropriate thermostatic bath, which allowed for operation over two temperature ranges, more or less from (210 to 290) K and from (290 to 360) K. The total volume of the cell, tubing, and pressure transducer cavity were estimated as (273.5 ± 0.3) cm3 at room temperature. A PID controller maintained the set temperature, which was measured with a 25 Ω platinum resistance thermometer (Hart Scientific 5680), possessing a total uncertainty of approximately 0.03 K. The uncertainty in the pressure measurements results from uncertainties in the transducer and indicator system and in the pressure gauges. The uncertainty of the pressure transducer/indicator (RUSKA7000) is 0.003 % of full scale (6000 kPa). Temperature fluctuations in the bath also affect the total pressure uncertainty. Regardless, the total pressure uncertainty was confirmed to be lower than 1 kPa. Taking into account the various uncertainties, the expanded uncertainty of the specific volume is estimated as lower than 0.005 m3·kg−1. To reduce the uncertainty in the measurement of the sample mass, the test sample was first charged into a bottle of a known tare weight. The combined mass of the bottle and sample were then measured using an analytical balance with an uncertainty of 0.3 mg. After placing the cell and connections under vacuum, the bottle was connected to the sphere, after which the bottle was once again weighed. In addition to this, the mass remaining in the connecting tube was estimated and subtracted from the discharged mass. This corrected value represents the sample mass. After reaching the set temperature, a mixing pump was activated for approximately 15 min after which the sample was allowed to stabilize for approximately 20 min before the data were recorded. After measuring the pressure at a given temperature, the thermostatic bath temperature was adjusted to the next test point.

the estimated saturated liquid densities. Both correlations were compared to other experimental data. In addition, the pressure in the superheated vapor region was measured along nine isochores for a large temperature range approximately from (243 to 373) K with an isochoric apparatus with an estimated expanded uncertainty of approximately 1 %. A Martin−Hou EoS was developed from the vapor-phase PvT data.



EXPERIMENTAL SECTION Materials. Table 1 describes the R1234ze(E) (trans-1,3,3,3tetrafluoroprop-1-ene, CF3CHCHF, CAS No. 29118-24-9) Table 1. R1234ze(E) Sample Description chemical name

source

initial mass fraction purity

purification method

R1234ze(E)a

Honeywell

0.995

none

a

trans-1,3,3,3-tetrafluoropropene.

tested. Noncondensable gases were eliminated by subjecting the sample to several iterations of freezing, evacuation, thawing, and ultrasonic stirring. Experimental Apparatus and Procedure: ITC−CNR. Subcooled liquid density measurements were made by means of an apparatus based on a stainless steel vibrating tube densimeter (Anton Paar DMA 512). The experimental apparatus and procedure are described in previous papers.30,31 Here, only the primary features of the experimental setup are described. The measurement principle is based on the relationship between the period of oscillation (Anton Paar mPDS 2000) of the vibrating U-tube densimeter and the sample density, which is determined through calibration at various temperatures and pressures. Pressure was measured with a piezo-resistive pressure gauge (Druck DPI 145) with an estimated experimental uncertainty of approximately 10 kPa. The temperature was controlled with a stability of about ± 0.003 K by means of a water thermostatic bath. Furthermore, an electrical resistance heater maintained fine control of the local temperature near the circuit connection, which ensured uniformity in the sample temperature and density in the vibrating tube. A Pt 100 Ω resistance thermometer with an estimated uncertainty of 0.05 K was used to measure the temperature. The densimeter was charged with the sample by means of a circuit of stainless steel tubes connecting the cell and the refrigerant canister. The fluid was pressurized with a syringe pump (Isco Pump, model 260D). A dedicated LabView based data acquisition system controlled the experimental apparatus and recorded the experimental variables. The total expanded uncertainty of the density measurements is estimated as approximately 0.8 kg·m−3. After purging and evacuating the system, liquid refrigerant was charged into the vibrating tube and associated measurement circuit. After stabilization of pressure and temperature, a controlled pressure decrease of about (10 to 15) kPa·s−1 was carried out through expansion of the syringe pump volume, while the periods of oscillation were acquired. The measurements for a single isotherm took approximately 14 400 s, including time needed for temperature adjustment and stabilization.



RESULTS AND DISCUSSION Experimental Subcooled Liquid Density. Herein, 14 099 new experimental subcooled liquid density data points for R1234ze(E) are provided for eight isotherms (283.15, 293.15, 303.15, 313.15, 323.15, 333.15, 343.15, and 353.15) K for P < 35 MPa. A selection of 270 data points is summarized in Table 2 and shown in Figure 1. All of the measured data are available in Supporting Information as described at the end of the paper. 3711

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Table 2. Selected Compressed Liquid Density Measurements for R1234ze(E) and Relative Deviations e = 100·Δρ/ρ = (ρcalc − ρexp)/ρexp of the Values Calculated (ρcalc) from eq 3 (Tait) or the Correlation of McLinden et al.15 (Ref), from the Experimental Values of This Work (ρexp)a T/K

P/MPa

ρ/kg·m−3

eTait/%

eref/%

283.15 283.15 283.15 283.15 283.15 283.15 283.15 283.15 283.15 283.15 283.15 283.15 283.15 283.14 283.15 283.14 283.15 283.14 283.14 283.15 283.15 283.14 283.14 283.15 283.15 283.15 283.14 283.14 283.14 283.15 283.14 283.14 283.14 283.15 293.15 293.15 293.14 293.14 293.15 293.15 293.15 293.15 293.15 293.14 293.14 293.14 293.14 293.14 293.15 293.15 293.14 293.14 293.14 293.15 293.14 293.14 293.15 293.14 293.15

34.022 33.020 32.017 31.009 30.001 28.987 27.984 26.982 25.966 24.959 23.948 22.932 21.921 20.909 19.891 18.876 17.875 16.870 15.859 14.841 13.827 12.805 11.789 10.765 9.760 8.745 7.725 6.721 5.710 4.689 3.662 2.638 1.620 0.619 34.035 33.027 32.027 31.009 30.001 28.993 27.991 26.985 25.973 24.957 23.953 22.938 21.921 20.900 19.891 18.879 17.857 16.853 15.838 14.835 13.830 12.817 11.799 10.798 9.788

1304.2 1302.1 1300.1 1297.8 1295.7 1293.4 1291.3 1289.1 1286.7 1284.4 1281.9 1279.6 1277.1 1274.5 1272.0 1269.4 1266.7 1263.9 1261.2 1258.4 1255.7 1252.4 1249.5 1246.5 1243.2 1240.0 1236.6 1233.2 1229.8 1226.1 1222.4 1218.5 1214.3 1210.5 1284.0 1281.7 1279.3 1277.1 1274.8 1272.4 1270.0 1267.4 1264.9 1262.3 1259.7 1257.2 1254.3 1251.6 1248.9 1246.2 1243.0 1240.1 1236.9 1233.8 1230.8 1227.5 1223.9 1220.7 1217.1

−0.024 −0.018 −0.017 −0.005 −0.010 0.002 −0.012 −0.009 −0.005 −0.008 0.007 −0.005 −0.006 0.001 0.000 0.002 0.007 0.016 0.005 0.002 −0.007 0.013 0.009 −0.003 0.011 0.007 0.003 0.003 −0.003 0.002 −0.003 −0.003 0.013 −0.011 0.006 0.013 0.028 0.018 0.018 0.015 0.018 0.031 0.035 0.037 0.038 0.026 0.041 0.033 0.030 0.019 0.038 0.027 0.036 0.034 0.020 0.022 0.035 0.018 0.019

0.135 0.136 0.133 0.142 0.132 0.141 0.124 0.123 0.124 0.118 0.130 0.114 0.112 0.117 0.114 0.113 0.116 0.124 0.113 0.107 0.098 0.118 0.113 0.100 0.115 0.111 0.109 0.109 0.103 0.109 0.106 0.107 0.125 0.101 0.095 0.098 0.110 0.095 0.091 0.085 0.085 0.094 0.095 0.095 0.094 0.080 0.092 0.083 0.078 0.065 0.084 0.073 0.082 0.080 0.067 0.070 0.083 0.068 0.072 3712

T/K

P/MPa

ρ/kg·m−3

eTait/%

eref/%

323.15 323.15 323.15 323.15 323.14 323.15 323.15 323.14 323.14 323.15 323.15 323.15 323.15 323.14 323.14 323.14 323.14 323.14 323.14 323.14 323.14 323.14 323.15 323.15 323.14 323.14 323.14 323.14 323.14 323.14 323.14 323.14 323.14 323.14 333.15 333.15 333.15 333.15 333.15 333.15 333.15 333.15 333.15 333.15 333.15 333.15 333.15 333.15 333.15 333.15 333.15 333.16 333.15 333.16 333.16 333.16 333.16 333.15 333.16

34.015 33.002 31.990 30.984 29.967 28.950 27.947 26.941 25.937 24.922 23.918 22.914 21.901 20.888 19.877 18.870 17.853 16.839 15.836 14.826 13.808 12.808 11.798 10.784 9.772 8.751 7.748 6.730 5.705 4.686 3.638 2.609 1.595 1.009 34.013 33.006 31.995 30.988 29.982 28.967 27.958 26.944 25.940 24.932 23.923 22.913 21.900 20.898 19.891 18.876 17.873 16.870 15.858 14.855 13.849 12.847 11.831 10.813 9.801

1222.6 1219.7 1216.9 1213.9 1210.9 1207.8 1204.7 1201.5 1198.3 1194.9 1191.5 1188.0 1184.5 1180.8 1177.0 1173.1 1169.1 1165.0 1160.8 1156.4 1151.8 1147.2 1142.3 1137.3 1131.9 1126.4 1120.7 1114.5 1108.0 1101.1 1093.6 1085.6 1077.1 1071.8 1202.3 1199.3 1196.1 1193.0 1189.8 1186.4 1183.0 1179.7 1176.1 1172.5 1168.8 1165.0 1161.0 1157.0 1152.9 1148.5 1144.2 1139.6 1134.8 1129.9 1124.8 1119.5 1114.0 1108.1 1102.0

−0.002 0.003 0.006 0.017 0.014 0.023 0.025 0.036 0.034 0.042 0.047 0.048 0.049 0.054 0.056 0.057 0.059 0.055 0.055 0.060 0.060 0.055 0.053 0.049 0.049 0.038 0.032 0.027 0.022 0.015 0.006 0.002 −0.001 −0.002 −0.057 −0.051 −0.044 −0.041 −0.034 −0.026 −0.022 −0.028 −0.018 −0.017 −0.013 −0.010 −0.003 −0.001 0.003 0.008 0.007 0.010 0.014 0.014 0.014 0.020 0.011 0.010 0.009

−0.042 −0.042 −0.044 −0.037 −0.043 −0.039 −0.040 −0.031 −0.036 −0.031 −0.029 −0.028 −0.029 −0.023 −0.021 −0.019 −0.016 −0.016 −0.014 −0.005 0.001 0.003 0.009 0.015 0.027 0.030 0.040 0.054 0.070 0.090 0.109 0.139 0.174 0.197 −0.124 −0.124 −0.121 −0.123 −0.122 −0.118 −0.118 −0.128 −0.122 −0.124 −0.123 −0.122 −0.116 −0.116 −0.111 −0.106 −0.106 −0.101 −0.094 −0.090 −0.084 −0.071 −0.071 −0.058 −0.047

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Table 2. continued T/K

P/MPa

ρ/kg·m−3

eTait/%

eref/%

T/K

P/MPa

ρ/kg·m−3

eTait/%

eref/%

293.14 293.14 293.14 293.14 293.14 293.15 293.14 293.14 293.14 303.15 303.15 303.15 303.14 303.14 303.14 303.14 303.14 303.14 303.14 303.14 303.14 303.14 303.14 303.14 303.14 303.14 303.14 303.14 303.14 303.14 303.14 303.14 303.14 303.14 303.13 303.13 303.14 303.14 303.13 303.14 303.14 303.13 303.13 313.15 313.15 313.15 313.15 313.15 313.14 313.15 313.14 313.14 313.15 313.14 313.14 313.14 313.14 313.14 313.14 313.15 313.14

8.772 7.761 6.755 5.738 4.727 3.682 2.650 1.644 0.778 33.993 32.984 31.972 30.966 29.958 28.955 27.943 26.942 25.928 24.920 23.916 22.909 21.899 20.888 19.875 18.856 17.845 16.838 15.824 14.819 13.809 12.794 11.778 10.775 9.773 8.772 7.769 6.764 5.757 4.747 3.716 2.678 1.676 0.802 34.013 33.010 32.010 31.006 30.002 28.984 27.973 26.971 25.962 24.948 23.947 22.937 21.923 20.909 19.890 18.874 17.865 16.855

1213.4 1209.7 1205.9 1201.8 1197.6 1193.3 1188.7 1184.2 1179.9 1264.4 1262.0 1259.5 1256.7 1254.5 1251.6 1249.1 1246.4 1243.5 1240.8 1238.0 1234.9 1232.0 1228.8 1225.8 1222.6 1219.4 1216.0 1212.5 1209.1 1205.3 1201.7 1197.9 1194.1 1190.0 1185.8 1181.3 1176.9 1172.2 1167.3 1162.3 1156.8 1151.1 1145.9 1243.6 1241.0 1238.4 1235.7 1232.9 1230.1 1227.2 1224.3 1221.3 1218.2 1215.2 1212.0 1208.7 1205.3 1201.9 1198.3 1194.7 1191.1

0.020 0.009 0.009 0.009 0.008 −0.005 −0.005 −0.016 −0.001 −0.093 −0.092 −0.088 −0.064 −0.085 −0.061 −0.067 −0.062 −0.049 −0.053 −0.056 −0.038 −0.040 −0.029 −0.038 −0.034 −0.037 −0.028 −0.025 −0.033 −0.013 −0.027 −0.026 −0.034 −0.027 −0.026 −0.014 −0.017 −0.015 −0.013 −0.026 −0.021 −0.012 0.001 −0.021 −0.017 −0.014 −0.010 −0.001 −0.003 0.001 0.009 0.010 0.014 0.013 0.017 0.022 0.022 0.025 0.028 0.028 0.025

0.075 0.068 0.071 0.076 0.078 0.069 0.075 0.069 0.089 −0.016 −0.019 −0.019 0.002 −0.023 −0.002 −0.011 −0.008 0.002 −0.004 −0.009 0.007 0.004 0.014 0.004 0.008 0.005 0.015 0.020 0.013 0.035 0.025 0.030 0.026 0.037 0.044 0.063 0.067 0.077 0.089 0.086 0.102 0.124 0.148 −0.037 −0.037 −0.039 −0.038 −0.033 −0.038 −0.037 −0.032 −0.034 −0.031 −0.034 −0.031 −0.028 −0.028 −0.025 −0.021 −0.020 −0.021

333.16 333.16 333.16 333.16 333.16 333.16 333.16 333.16 333.16 343.15 343.15 343.15 343.15 343.15 343.15 343.15 343.15 343.15 343.15 343.15 343.15 343.15 343.15 343.15 343.15 343.15 343.16 343.15 343.16 343.16 343.15 343.15 343.15 343.15 343.15 343.15 343.15 343.15 343.15 343.15 343.15 343.15

8.801 7.784 6.767 5.766 4.755 3.721 2.698 1.683 1.380 33.994 32.989 31.987 30.968 29.953 28.947 27.938 26.933 25.929 24.913 23.913 22.905 21.883 20.877 19.867 18.851 17.849 16.838 15.829 14.817 13.798 12.788 11.770 10.753 9.736 8.731 7.717 6.697 5.696 4.690 3.648 2.607 1.625

1095.7 1088.8 1081.5 1073.9 1065.6 1056.4 1046.3 1035.2 1031.7 1180.8 1177.5 1174.2 1170.7 1167.2 1163.6 1160.0 1156.2 1152.4 1148.4 1144.3 1140.2 1135.8 1131.4 1126.8 1122.0 1117.1 1112.0 1106.7 1101.1 1095.3 1089.2 1082.8 1076.1 1068.9 1061.4 1053.2 1044.5 1035.1 1024.7 1012.8 999.1 984.2

0.003 0.002 0.000 −0.008 −0.014 −0.020 −0.012 0.000 −0.001 −0.114 −0.103 −0.097 −0.093 −0.085 −0.080 −0.075 −0.070 −0.062 −0.058 −0.047 −0.047 −0.038 −0.042 −0.033 −0.032 −0.025 −0.026 −0.023 −0.022 −0.016 −0.021 −0.022 −0.025 −0.024 −0.033 −0.035 −0.043 −0.048 −0.054 −0.053 −0.038 −0.001

−0.036 −0.018 0.004 0.023 0.049 0.080 0.130 0.188 0.202 −0.114 −0.110 −0.110 −0.110 −0.108 −0.107 −0.108 −0.107 −0.104 −0.103 −0.095 −0.097 −0.091 −0.097 −0.089 −0.088 −0.081 −0.080 −0.073 −0.069 −0.057 −0.053 −0.045 −0.035 −0.019 −0.009 0.012 0.030 0.056 0.083 0.120 0.172 0.227

353.15 353.15 353.15 353.14 353.15 353.15 353.15 353.15 353.15 353.15 353.16 353.15 353.15 353.16 353.15 353.15 353.16 353.15

33.998 32.983 31.977 30.961 29.957 28.953 27.950 26.934 25.928 24.907 23.896 22.889 21.883 20.878 19.865 18.850 17.837 16.834

1159.9 1156.3 1152.7 1149.0 1145.2 1141.4 1137.5 1133.3 1129.2 1124.7 1120.3 1115.7 1111.0 1106.1 1101.0 1095.7 1090.2 1084.4

0.009 0.014 0.018 0.021 0.028 0.029 0.030 0.038 0.037 0.048 0.049 0.047 0.051 0.055 0.056 0.052 0.057 0.061

−0.153 −0.152 −0.150 −0.150 −0.147 −0.148 −0.149 −0.144 −0.147 −0.137 −0.138 −0.138 −0.134 −0.131 −0.127 −0.127 −0.120 −0.110

3713

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Table 2. continued

a

T/K

P/MPa

ρ/kg·m−3

eTait/%

eref/%

T/K

P/MPa

ρ/kg·m−3

eTait/%

eref/%

313.14 313.14 313.14 313.14 313.14 313.14 313.14 313.14 313.14 313.14 313.14 313.15 313.14 313.14 313.14 313.14

15.848 14.845 13.831 12.819 11.816 10.800 9.798 8.784 7.763 6.749 5.739 4.723 3.683 2.657 1.656 0.775

1187.2 1183.4 1179.3 1175.2 1170.9 1166.5 1161.9 1157.1 1152.1 1146.8 1141.4 1135.7 1129.4 1122.9 1116.2 1109.9

0.029 0.027 0.026 0.022 0.025 0.019 0.017 0.016 0.010 0.010 0.000 −0.003 0.001 −0.002 −0.002 −0.001

−0.015 −0.014 −0.011 −0.009 0.000 0.000 0.007 0.016 0.021 0.033 0.037 0.050 0.073 0.090 0.113 0.135

353.15 353.16 353.16 353.15 353.16 353.16 353.15 353.16 353.16 353.16 353.16 353.16 353.16 353.16 353.15

15.825 14.816 13.815 12.814 11.799 10.794 9.793 8.789 7.775 6.749 5.740 4.723 3.704 2.681 2.236

1078.4 1072.2 1065.7 1058.8 1051.4 1043.6 1035.4 1026.5 1016.7 1005.9 994.0 980.5 964.9 945.9 936.2

0.062 0.057 0.056 0.052 0.045 0.045 0.031 0.023 0.007 −0.008 −0.022 −0.038 −0.049 −0.025 −0.004

−0.102 −0.101 −0.093 −0.082 −0.078 −0.059 −0.051 −0.035 −0.023 −0.001 0.024 0.051 0.079 0.122 0.135

Standard uncertainties are u(T) = 0.05 K, u(P) = 1 kPa, and u(ρ) = 0.8 kg·m−3.

Figure 2. Relative deviations Δρs/ρs = (ρs,calc1 − ρs,calc2)/ρs,calc2 of the values obtained from eq 2 (ρs,calc1) from the values obtained from the correlation of McLinden et al.15 (ρs,calc2) for R1234ze(E).

Figure 1. Measured compressed liquid densities by the authors for R1234ze(E); ●, 283.15 K; ○, 293.15 K; ▼, 303.15 K; △, 313.15 K; ■, 323.15 K; □, 333.15 K; ▲, 343.15 K; ▽, 353.15 K; −, eq 2.

Table 3. Constants for eq 1 from Di Nicola et al.11 A1

A2

A3

A4

−7.5046

1.5524

−2.2353

−4.1018

Table 4. Constants for eq 2 B1

B2

B3

B4

1.97456

0.13317

0.82384

−0.21152

The experimental data are used to develop a saturated liquid density correlation, which is compared to the correlation of McLinden et al.15 The data also are used to develop a subcooled liquid density correlation, which is compared to the correlation of McLinden et al.,15 the data of Table 2, and literature data.13−17 However, before discussing the development of these correlations, the critical state properties and a vapor pressure correlation will be briefly discussed since these are necessary for both density correlations. Critical State Properties. Experimentally measured values of critical temperature (Tc) = 382.51 ± 0.01 K, critical pressure

Figure 3. Relative deviations Δρs/ρs = (ρs,calc − ρs,exp)/ρs,exp of the values obtained from eq 2 (ρs,calc) from the experimental data from the literature11,12 (ρs,exp) for R1234ze(E); ○, Higashi et al.;12 ●, Grebenkov et al.13

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Table 5. Constants for eqs 3 and 4 C

a

b

d

e

0.083

−29.450

193.449

−419.699

341.446

Figure 6. Relative deviations Δρ/ρ = (ρcalc − ρexp)/ρexp of the values obtained from eq 3 (ρcalc) from the experimental data from the literature12−16 (ρexp) for R1234ze(E): △, Grebenkov et al.;12 ▼, Kayukawa et al.;13 ●, McLinden et al.;15 ○, Tanaka et al.;16 ×, Matsuguchi et al.17

Figure 4. Relative deviations Δρ/ρ = (ρcalc − ρexp)/ρexp of the values obtained from eq 3 (ρcalc) from the experimental data of this work (ρexp) for R1234ze(E); ●, 283.15 K; ○, 293.15 K; ▼, 303.15 K; △, 313.15 K; ■, 323.15 K; □, 333.15 K; ▲, 343.15 K; ▽, 353.15 K.

Figure 7. Relative deviations Δρ/ρ = (ρcalc1 − ρcalc2)/ρcalc2 of the values obtained from eq 3 (ρcalc1) from the value obtained from the correlation of McLinden et al.15 (ρcalc2) for R1234ze(E). Figure 5. Relative deviations Δρ/ρ = (ρcalc −ρexp)/ρexp of the values obtained from the correlation of McLinden et al.15 (ρcalc) from the experimental data of this work (ρexp) for R1234ze(E); ●, 283.15 K; ○, 293.15 K; ▼, 303.15 K; △, 313.15 K; ■, 323.15 K; □, 333.15 K; ▲, 343.15 K; ▽, 353.15 K.

ρs = ρc (1 + B1τ1/3 + B2 τ 2/3 + B3τ + B4 τ 4/3)

with the constants provided in Table 4. Equation 2 was developed by first fitting the data for each isotherm for P < 5 MPa with a third-order polynomial. These polynomials were coupled with eq 1 to provide estimates for ρs, which were then used to develop eq 2. Figure 2 shows percentage deviations (Δρs/ρs = (ρs,calc1 − ρs,calc2)/ρs,calc2) between eq 2 (ρs,calc1) and the correlation of McLinden et al.15 (ρs,calc2) for Ts = (240 to 380) K. For this temperature range, Δρs/ρs = (−0.23 to 0.13) %, with a with a mean absolute deviation (|100·Δρs/ρs|) of 0.144. Figure 3 shows percentage deviations (Δρs/ρs = (ρs,calc − ρs,exp)/ρs,exp) between eq 2 (ρs,calc) and literature data12,13 (ρs,exp) for Ts = (240 to 380) K. For the entire temperature range, Δρs/ρs = (−0.76 to 0.74) %; however, for Ts = (360 to 370) K, Δρs/ρs = (−0.31 to 0.04) %. Subcooled Liquid Density Correlation. The subcooled liquid density data were used to develop a Tait correlation given in eq 3.

(Pc) = 3632 kPa ± 3 kPa, and critical density (ρc) = 485 ± 3 kg/m3 have been reported.12 Vapor Pressure Correlations. Di Nicola et al.11 provide a Wagner vapor pressure correlation (reproduced in eq 1), which fits the data of Di Nicola et al.,11 McLinden et al.,15 and Tanaka et al.16 with a mean absolute deviation (|100·ΔP/P|) of 0.049. Tr ln(Pr) = A1τ + A 2 τ1.5 + A3τ 2.5 + A4 τ 5

(2)

(1)

with the constants provided in Table 3 and where the reduced temperature Tr = Ts/Tc, the reduced pressure Pr = Ps/Pc, τ = 1 − Tr, Ts = saturation temperature, and Ps = saturation pressure. Saturated Liquid Density Correlation. The subcooled liquid density data were used to develop the saturated liquid density (ρs) correlation given in eq 2. 3715

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Table 6. PvT Measurements in the Vapor Phase for R1234ze(E) and Relative Deviations e = 100·Δρ/ρ = (ρcalc − ρexp)/ρexp of the Values Calculated (ρcalc) from eq 5 (M-H) or the Correlation of McLinden et al.15 (Ref), from the Experimental Values of This Work (ρexp)a T/K

P/kPa

v/m3·kg−1

eM‑H/%

eref/%

T/K

P/kPa

v/m3·kg−1

eM‑H/%

eref/%

242.91 242.91 252.89 252.90 262.90 262.91 272.84 272.85 293.15 293.16 282.63 282.63 302.67 302.67 312.80 312.80 323.10 323.10 333.07 333.07 343.03 343.04 353.01 353.02 362.94 362.94 372.90 372.90

56.6 56.7 59.4 59.4 62.0 61.9 64.4 64.4 69.4 69.4 66.9 66.9 71.8 71.8 74.3 74.3 76.8 76.8 79.2 79.2 81.6 81.7 84.1 84.1 86.6 86.6 89.1 89.1

0.301 0.301 0.301 0.301 0.302 0.302 0.302 0.302 0.302 0.302 0.302 0.302 0.302 0.302 0.302 0.302 0.302 0.302 0.302 0.302 0.303 0.303 0.303 0.303 0.303 0.303 0.303 0.303

1.146 1.133 0.660 0.659 0.381 0.405 0.318 0.320 0.189 0.184 0.194 0.180 0.119 0.147 0.105 0.104 0.062 0.057 0.034 0.036 0.009 −0.007 −0.070 −0.067 −0.200 −0.201 −0.220 −0.219

0.886 0.874 0.490 0.490 0.283 0.307 0.272 0.273 0.210 0.206 0.185 0.172 0.159 0.187 0.155 0.154 0.117 0.112 0.088 0.091 0.059 0.043 −0.027 −0.025 −0.167 −0.169 −0.199 −0.199

292.83 292.83 302.78 302.78 312.76 312.76 323.10 323.10 333.07 333.07 343.04 343.04 352.99 352.99 362.96 362.96 372.89 372.90

415.4 415.4 433.9 433.9 451.9 452.0 470.5 470.5 488.2 488.2 505.6 505.6 522.8 522.8 540.0 540.0 557.0 557.0

0.045 0.045 0.045 0.045 0.046 0.046 0.046 0.046 0.046 0.046 0.046 0.046 0.046 0.046 0.046 0.046 0.046 0.046

0.273 0.270 0.104 0.104 0.040 0.039 0.011 0.011 0.020 0.018 0.059 0.062 0.147 0.143 0.218 0.220 0.313 0.312

0.267 0.262 0.266 0.266 0.308 0.308 0.336 0.336 0.361 0.359 0.383 0.387 0.433 0.428 0.446 0.448 0.470 0.468

302.67 302.67 312.72 312.72 323.11 323.11 333.08 333.08 343.04 343.04 353.00 353.01 362.96 362.96 372.91 372.91 262.94 262.95 272.87 272.87 282.60 282.60 292.54 292.54 302.69

162.7 162.7 168.6 168.6 174.6 174.6 180.4 180.4 186.1 186.1 191.9 191.9 197.6 197.6 203.3 203.3 139.4 139.4 145.5 145.5 151.4 151.4 157.2 157.2 162.7

0.131 0.131 0.131 0.131 0.131 0.131 0.131 0.131 0.131 0.131 0.131 0.131 0.131 0.131 0.131 0.131 0.130 0.130 0.131 0.131 0.131 0.131 0.131 0.131 0.131

−0.060 −0.073 −0.138 −0.152 −0.159 −0.163 −0.180 −0.174 −0.190 −0.193 −0.204 −0.206 −0.230 −0.224 −0.211 −0.203 0.134 0.141 −0.109 −0.102 −0.227 −0.235 −0.304 −0.317 −0.061

0.020 0.007 −0.030 −0.042 −0.036 −0.040 −0.055 −0.049 −0.074 −0.078 −0.105 −0.106 −0.155 −0.150 −0.158 −0.152 −0.127 −0.114 −0.240 −0.232 −0.258 −0.266 −0.268 −0.280 0.025

312.60 312.59 325.11 325.11 333.09 333.09 343.04 343.04 353.00 353.00 362.96 362.96 372.97 372.97

574.7 574.7 605.5 605.5 624.8 624.8 648.5 648.5 672.0 672.1 695.3 695.3 718.6 718.5

0.035 0.035 0.035 0.035 0.035 0.035 0.035 0.035 0.035 0.035 0.035 0.035 0.035 0.035

0.078 0.074 0.002 0.001 0.001 0.003 0.048 0.046 0.113 0.111 0.208 0.207 0.311 0.316

0.391 0.388 0.416 0.417 0.436 0.437 0.469 0.468 0.489 0.486 0.512 0.511 0.522 0.528

313.13 313.13 323.11 323.11 333.09 333.09 343.06 343.06 353.01 353.02 362.98 362.98 372.92 372.92

630.4 630.3 658.4 658.4 685.9 685.9 713.0 713.1 739.8 739.8 766.3 766.3 792.3 792.3

0.031 0.031 0.031 0.031 0.031 0.031 0.031 0.031 0.031 0.031 0.031 0.031 0.031 0.031

−0.221 −0.217 −0.337 −0.340 −0.384 −0.381 −0.379 −0.383 −0.337 −0.338 −0.268 −0.267 −0.167 −0.169

0.112 0.116 0.096 0.095 0.087 0.091 0.082 0.078 0.076 0.075 0.068 0.068 0.070 0.068

282.66 282.66 292.56 292.56

238.8 238.8 248.7 248.8

0.080 0.080 0.080 0.080

−0.095 −0.091 −0.247 −0.254

−0.177 −0.172 −0.210 −0.218

324.12 324.12 333.09 333.09 343.15 343.15 353.00 353.00 362.97 362.97

770.9 771.0 801.4 801.3 834.9 835.0 867.3 867.3 899.7 899.7

0.026 0.026 0.026 0.026 0.026 0.026 0.026 0.026 0.026 0.026

0.021 0.016 0.000 0.003 0.032 0.030 0.112 0.114 0.229 0.227

0.519 0.515 0.549 0.552 0.578 0.576 0.607 0.609 0.637 0.635

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Table 6. continued

a

T/K

P/kPa

v/m3·kg−1

eM‑H/%

eref/%

T/K

P/kPa

v/m3·kg−1

eM‑H/%

eref/%

302.54 302.54 312.84 312.84 323.10 323.10 333.07 333.07 343.03 343.03 352.95 352.96 362.94 362.94 372.90 372.90

258.6 258.5 268.5 268.5 278.4 278.4 288.0 288.0 297.5 297.5 306.8 306.9 316.3 316.2 325.6 325.6

0.080 0.080 0.080 0.080 0.081 0.081 0.081 0.081 0.081 0.081 0.081 0.081 0.081 0.081 0.081 0.081

−0.321 −0.314 −0.339 −0.340 −0.345 −0.347 −0.339 −0.339 −0.319 −0.324 −0.282 −0.286 −0.240 −0.237 −0.198 −0.192

−0.203 −0.196 −0.169 −0.168 −0.151 −0.153 −0.140 −0.141 −0.133 −0.138 −0.122 −0.126 −0.113 −0.110 −0.113 −0.108

372.96 372.96

931.7 931.7

0.026 0.026

0.371 0.367

0.663 0.659

323.12 323.12 333.09 333.10 343.06 343.06 353.03 353.03 362.97 362.98 372.95 372.95

836.8 836.8 875.5 875.5 913.5 913.4 950.8 950.8 987.6 987.6 1023.8 1023.9

0.023 0.023 0.023 0.023 0.023 0.023 0.023 0.023 0.023 0.023 0.023 0.023

−0.042 −0.043 −0.115 −0.117 −0.111 −0.107 −0.051 −0.049 0.045 0.050 0.193 0.189

0.473 0.472 0.476 0.474 0.485 0.489 0.494 0.496 0.497 0.501 0.523 0.521

292.76 302.78 312.61 312.61 312.61 323.11 323.11 333.09 333.09 343.05 343.05 353.01 353.01 362.95 362.96 372.93 372.93

366.1 381.8 397.2 397.1 397.1 413.3 413.4 428.5 428.5 443.5 443.5 458.4 458.4 473.2 473.2 488.0 488.0

0.052 0.052 0.052 0.052 0.052 0.052 0.052 0.052 0.052 0.052 0.052 0.052 0.052 0.053 0.053 0.053 0.053

0.420 0.309 0.221 0.223 0.226 0.172 0.167 0.175 0.177 0.194 0.196 0.228 0.229 0.273 0.274 0.338 0.334

0.434 0.463 0.462 0.464 0.469 0.461 0.456 0.475 0.476 0.479 0.480 0.478 0.477 0.469 0.472 0.473 0.467

Standard uncertainties are u(T) = 0.03 K, u(P) = 1 kPa, and u(ρ) = 0.005 kg·m−3.

with ρs given by eq 2, β given by eq 4, β = Pc( −1 + aτ1/3 + bτ 2/3 + dτ + eτ 4/3)

and the constants provided in Table 5. Figure 4 shows percentage deviations (Δρ/ρ = (ρcalc − ρexp)/ ρexp) between eq 3 (ρcalc) and the data of Table 2 (ρexp). For the isotherms T = (283.15, 293.15, 303.15, 313.15, 323.15, 333.15, 343.15, and 353.15) K, Δρ/ρ = (−0.11 to 0.06) %, with a mean absolute deviation (|100·Δρ/ρ|) of 0.027. Figure 5 shows percentage deviations (Δρ/ρ = (ρcalc − ρexp)/ ρexp) between the correlation of McLinden et al.15 (ρcalc) and the data of Table 2 (ρexp). For the isotherms T = (283.15, 293.15, 303.15, 313.15, 323.15, 333.15, 343.15, and 353.15) K, Δρ/ρ = (−0.15 to 0.23) %. The correlation of McLinden et al.15 has a declared liquid density uncertainty of 0.1 % from (240 to 320) K and pressures to 10 MPa, while it increases up to 0.5 % outside these boundaries. Note that, in addition to providing T, P, and ρ, Table 2 shows relative percentage deviations for the Tait correlation (eq 3) and the McLinden et al.15 correlation compared to the measured data. Figure 6 shows percentage deviations (Δρ/ρ = (ρcalc − ρexp)/ ρexp) between eq 3 (ρcalc) and literature data13−17 (ρexp). The mean absolute percentage deviations (|Δρ/ρ|) for Grebenkov et al.,13 Kayukawa et al.,14 McLinden et al.,15 Tanaka et al.,16

Figure 8. Measured PvT data in the vapor phase by the authors for R1234ze(E): ●, 0.302 m3·kg−1; ○, 0.131 m3·kg−1; ▼, 0.080 m3·kg−1; △, 0.052 m3·kg−1; ■, 0.045 m3·kg−1; □, 0.035 m3·kg−1; ▲, 0.031 m3·kg−1; ▽, 0.026 m3·kg−1; ×, 0.023 m3·kg−1; −, eq 5.

⎡ ⎛ β + P ⎞⎤ ρ−1 = ρs−1⎢1 − C ln⎜ ⎟⎥ ⎢⎣ ⎝ β + Ps ⎠⎥⎦

(4)

(3)

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Table 7. Constants for eq 5 Tc

R

b

A2

B2

C2

K

kJ·kg−1·K−1

m3·kg−1

kJ·m3·kg−2

kJ·m3·kg−2·K−1

kJ·m3·kg−2

0.000319566

−0.640936 B5

382.51 A3 kJ·m6·kg−3 0.000423719

0.0729083

−0.205458

0.00034514 B3

kJ·m6·kg−3·K−1 −7.720294·10

−7

C3

A4

kJ·m6·kg−3

kJ·m9·kg−4

0.00103922

kJ·m12·kg−5·K−1 −7

−1.029544·10

8.399027·10−14

Figure 11. Relative deviations ΔP/P = (Pcalc − Pexp)/Pexp of the values obtained from eq 5 (Pcalc) from the experimental data from the literature12−14,17 (Pexp) for R1234ze(E); △, Grebenkov et al.;13 ▼, Kayukawa et al.;14 ●, McLinden et al.;15 ○, Tanaka and Higashi.18

Figure 9. Relative deviations ΔP/P = (Pcalc − Pexp)/Pexp of the values obtained from eq 5 (Pcalc) from the experimental data of this work (Pexp) for R1234ze(E); ●, 0.3021 m3·kg−1; ○, 0.1307 m3·kg−1; ▼, 0.0805 m3·kg−1; △, 0.0524 m3·kg−1; ■, 0.0455 m3·kg−1; □, 0.0346 m3·kg−1; ▲, 0.0312 m3·kg−1; ▽, 0.0259 m3·kg−1; ×, 0.0233 m3·kg−1.

Figure 12. Relative deviations ΔP/P = (Pcalc1 − Pcalc2)/Pcalc2 of the values obtained from eq 5 (Pcalc1) from the value obtained from the correlation of McLinden et al.15 (Pcalc2) for R1234ze(E); v varies from (0.00438 to 0.2806) m3·kg−1, doubling each step, while the temperature varies from Ts to 380 K for each step.

Figure 10. Relative deviations ΔP/P = (Pcalc − Pexp)/Pexp of the values obtained from the correlation of McLinden et al.14 (Pcalc) from the experimental data of this work (Pexp) for R1234ze(E); ●, 0.3021 m3·kg−1; ○, 0.1307 m3·kg−1; ▼, 0.0805 m3·kg−1; △, 0.0524 m3·kg−1; ■, 0.0455 m3·kg−1; □, 0.0346 m3·kg−1; ▲, 0.0312 m3·kg−1; ▽, 0.0259 m3·kg−1; ×, 0.0233 m3·kg−1.

Experimental PvT Data in the Vapor Phase. Herein, 160 new experimental vapor-phase PvT data for R1234ze(E) are provided for nine isochores of (0.3021, 0.1307, 0.0805, 0.0524, 0.0455, 0.0346, 0.0312, 0.0259, and 0.0233) m3·kg−1 for T < 380 K. The data are summarized in Table 6 and shown in Figure 8. The experimental data are used to develop a Martin-Hou EoS for the vapor phase for T < Tc and P < Pc, which is compared to the data of Table 6, the FEQ Helmholtz EoS of McLinden et al.,15 and literature data.

and Matsuguchi et al.17 are (0.25, 1.16, 0.10, 0.13, and 2.15) %, respectively. Thus, the data of Kayukawa et al.14 and Matsuguchi et al.17 appear to be inconsistent with the other data sets. Figure 7 shows percentage deviations (Δρ/ρ = (ρcalc1 − ρcalc2)/ρcalc2) of eq 3 (ρcalc1) relative to the correlation of McLinden et al.15 (ρcalc2). For the entire temperature range, Δρ/ρ = (−0.25 to 0.19) %. 3718

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PvT Correlation in the Vapor Phase. A Martin-Hou EoS (eq 5) valid in the vapor phase was developed from the vaporphase PvT data. P=

herein, 301 data points from three different research groups, and the correlation of McLinden et al.15 as implemented in Refprop 9.0. The Martin−Hou equation of state provided in eq 5 has percentage deviations for Tr = (0.63 to 0.99) relative to the experimental data of Table 6 of ΔP/P = (−0.35 to 1.03) % and for Tr = (0.68 to 0.99) of ΔP/P = (−0.35 to 0.38) %. For the same temperature ranges, eq 5 has percentage deviations relative to the correlation of McLinden et al.15 of ΔP/P = (−0.28 to 0.89) % and ΔP/P = (−0.28 to 0.66) %, respectively.

A + B2 T + C2e−5.475T / Tc RT + 2 v−b (v − b)2 +

A3 + B3T + C3e−5.475T / Tc 3

(v − b)

+

A4 4

(v − b)

+

B5T (v − b)5



(5)

ASSOCIATED CONTENT

S Supporting Information *

with the constants provided in Table 7, P is in kPa, v is in m3·kg−1, and T is in K. Figure 9 shows percentage deviations (ΔP/P = (Pcalc − Pexp)/ Pexp) between eq 5 (Pcalc) and the data of Table 6 (Pexp). For the isochores v = (0.3021, 0.1307, 0.0805, 0.0524, 0.0455, 0.0346, 0.0312, 0.0259, and 0.0233) m3·kg−1, Δ P/P = (−0.35 to 1.03) % for T = (240 to 380) K; however, ΔP/P = (−0.35 to 0.38) % for T = (260 to 380) K, with a mean absolute deviation (|100·ΔP/P |) of 0.198 over the entire temperature range. Figure 10 shows percentage deviations (ΔP/P = (Pcalc − Pexp)/Pexp) between the correlation of McLinden et al.15 (Pcalc) and the data of Table 6 (Pexp). For the isochores v = (0.302, 0.131, 0.080, 0.052, 0.045, 0.035, 0.031, 0.026, and 0.023) m3·kg−1, ΔP/P = (−0.28 to 0.89) % for T = (240 to 380) K; however, ΔP/P = (−0.28 to 0.66) % for T = (260 to 380) K. Figure 11 shows percentage deviations (ΔP/P = (Pcalc − Pexp)/Pexp) between eq 5 (Pcalc) and literature data13−17 (Pexp). The mean absolute percentage deviations (|ΔP/P|) for Grebenkov et al.,13 Kayukawa et al.,14 McLinden et al.,15 and Tanaka and Higashi18 are (1.85, 1.11, 0.63, and 0.56) %, respectively. Thus, the data of Grebenkov et al.13 and Kayukawa et al.14 appear to be inconsistent with the other data sets. Figure 12 shows percentage deviations (ΔP/P = (Pcalc1 − Pcalc2)/Pcalc2) of eq 5 (Pcalc1) relative to the correlation of McLinden et al.15 (Pcalc2). For the entire PvT range, ΔP/P = (−0.79 to 0.15) %.

All experimental data. This material is available free of charge via the Internet at http://pubs.acs.org.



AUTHOR INFORMATION

Corresponding Author

*Tel.: +39 049 8295831. Fax: +39 049 8295728. E-mail: laura. [email protected]. Notes

The authors declare no competing financial interest.

■ ■

ACKNOWLEDGMENTS The authors thank Andrea Ferron for his assistance and Honeywell for donating the sample. REFERENCES

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CONCLUSIONS Some 14 099 subcooled liquid density measurements of R1234ze(E) (1,3,3,3-tetrafluoroprop-1-ene; CF3CHCHF) for reduced temperatures from (0.74 to 0.92) for reduced pressures less than 9.6 are presented, which is a far broader experimental pressure range than the existing literature data. The data were used to develop a saturated liquid density correlation and a subcooled liquid density correlation (Tait equation), which were compared to the experimental points presented herein, 163 data points from five different research groups, and the correlation of McLinden et al. 15 as implemented in Refprop 9.0. The saturated liquid density correlation provided in eq 2 has percentage deviations for Tr = (0.63 to 0.99) relative to the correlation of McLinden et al.15 of Δρs/ρs = (−0.23 to 0.13) %. The subcooled liquid density correlation provided in eq 3 has percentage deviations for Tr = (0.74 to 0.92) relative to the experimental data of Table 2 of Δρ/ρ = (−0.11 to 0.06) % and for the same temperature range has percentage deviations relative to the correlation of McLinden et al.15 of Δρ/ρ = (−0.25 to 0.19) %. Some 160 PvT measurements in the vapor phase of R1234ze(E) for nine isochores for reduced temperatures less than 0.99 are presented. The data were used to develop a Martin−Hou equation of state valid for T < Tc and P < Pc. The correlation is compared to the experimental points presented 3719

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